Valuable hydrocarbon products



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/ VALUAELE ZKYIDRQQARBON PEG'DUCTS Michaei Otto and. Martin ltiuellen-tiunradi, Lud

Rhine, Germany, assiznors to E. Farhe'nindusttie dirtiengeeellschatt, Frankfort cn themriain, Germany ,No Drawing. Originai application July 21, 1932,

Serial No. 623,812.

many July 25, 1931 Divided and this application June 20, 1938, Serial No. 676,680.

In Ger- Claims. (01. ice-151) This is a divisional application of our application Ser. No. 623,812, filed July 21st, 1932, which relates to the preparation of valuable hydrocarbon products, more particularly those of higher boiling point.

We have found that hydrocarbon mixtures, in particular those having a boiling point above 200 C., and especially those boiling above about 325 C. at ordinary pressure, for example lubril0 eating oils or greases or hard or soft parafiln wax,

are considerably improved and that in particular the viscosity of these materials is much increased by adding thereto high molecular hydrocarbons having a molecular weight of for example 1000 or 2000 or even more measured by the eflect of markably flattened in many cases. Furthermore the hydrocarbon mixtures is increased to double the material on the boiling or freezing point of benzol. winch are obtained by polymerizing isoolefines and in particular iso-butylene.

the addition of these high molecular hydrocarbons obtained by polymerizing iso-olefines (which hydrocarbons for the sake of brevity are hereinafter referred to as polymerized iso-olefines) also the temperature-viscosity curve of the hydrocarbon mixture to be improved is rethe electric properties of these hydrocarbon mix tures are considerably changed so that for example by the addition of only 1 per cent of polymerized iso-olefines the disruptive strength of switches. Hard and soft paraflln wax is rendered transparent by the addition of the said polymerized iso-olefines; furthermore the formation of fissures and cracks is prevented thereby. In

many cases it is suflicient to add the polymer- A 40 ized iso-olefines in an amount of from a fraction of one per cent up to about 10 per cent with reference to the hydrocarbon mixtures to be improved, but the amount added may also be much higher, as for example about 20 or 35 or even 545 per cent.

For many purposes, as for example for lubrieating automobile motors, it is well known that oils are necessary which on the one hand still have a satisfactory viscosity at high tempera- 5'0 tures, as for example from to 150 C., and;

on the other hand are still so thinly liquid at low temperatures that the friction is not too great for the automobile motor to be set in motion directly by thestarting device. According to 55 the'present invention oils can be prepared which correspond to a great extent to these require ments and which are far superior to the special automobile oils hitherto in commerce.

The effect of the addition of the said polymerized iso-olefines is shown in the following table of examples. The oils used in experiments A, B, C, D, and E are mineral oils of the type of the commercial light to medium machine oils. Experiments A, B, C, C", D, and E show the efiect of the addition of an iso-butylene polymerization product. Experiments F, G, and H are the tests of special automobile oils. In all cases the temperatures are given in degrees C.

The viscosity index indicates the value of the oil in that as the index value increases, the qual ity of the oil improves.

Percentage Viscosity in Englcr at isobutylenc Expt. pplytrlner- I 011 o o o o o 0 product 0 20 38 50 100 A 0 125 25 8.3 1.6 Below 1.2 A 0 42 15.6 8.8 2.25 1:44 B 0 40 11 5.3 3.0 1.45 Below 1.2 B' 4 98 29.5129 7.7 2.25 1.47 O 0 3.3 2.1 1.3 C' 4 110 33 13.0 8.2 2.32 1.43 C- 13 280 84 36.2 21.8 5.0 2.18 D 0 12 4.8 2.55 2.0 1.3 0 55 20.5 9.8 6.5 2.25 1.52 0 41 12.0 7.0 1.8 1.22 1 About 280 58 10.1 10.3 2.3 1.42 0 About300 53 21.2 11.1 2.3 1.4 0 Over 300 73.52L8 11 2.12 1.32 0 Over 300 83 25.3 13 2.5 1.45

Viscosity Setting Flash- Density Ekpt' index point point at 20 From the table it can be seen that the addition of the highly polymerized isobutylene products considerably improves the oils.. The resulting improved oils have even a higher viscosity index than special automobile oils or high value.

On account of the low coke test of the polymerized iso-oleflnes the lubricating oils the viscosity sudden superheating.

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of which has been incremd by the addition of the said polymerized iso-oleflnes instead of by Vlscosit Oonradson Additions at coke test 1. 66 0.08 4.0 percent of l erlzed isobutylene. 3. 0 0. 09 83.0 percent 0 br ght stock oil l. 0 0. 52 33.0 percent of hot steam cylinder oil 1. 0 0. 71

The effect of the addition of polymerized isoolefines to greases is shown by the following example:

1200 grams of a lubricating oil for freezing machines having a viscosity of 7 Engler at 20 C. and a setting point of 45 below zero C. is mixed after dissolution therein of 60 grams of polymerized isobutylene with 250 grams of oleic acid glyceride, 30 grams of hydrate of lime and 20 grams of a 20 per cent solution of caustic soda, the mixture being stirred for about 5 hours at 100 C. The resulting grease is soft and of a great adhesive power.

-Also hard and soft parafiin wax is considerably improved by the addition of polymerized isobutylene as will be seen from the following example:

Polymerized isobutylene is added in an amount of from 1 to 4 per cent to paraffin wax having a strong tendency to form crystals and which when employed for casting candles causes the formation of fissures. The candles cast with the mixture thus obtained do not show fissures to a substantial degree and fissures or points of crystallization still formed disappear after 1 or 2 days. The candles are uniformly transparent.

- The production of the polymerized iso-olefines to be added to the hydrocarbon products is effected by polymerization of the iso-olefines in the presence of suitable catalysts, preferably Volatilizable inorganic halides, such as boron fluoride, boron fluoride charged with hydro fluoric acid, phosphorus tri-fluoride, phosphorus pentafluoride, aluminum chloride, preferably in statu nascendi, such as aluminum chloride as is formed by allowing hydrogen chloride to act on aluminium, or solutions or double compounds of the said halides, while cooling so strongly that no sudden substantial increase in temperature occurs. The said catalysts may be employed as such or together with substances such as phenol or cresol, in which they dissolve without decomposition, whether with the formation of real solutions, or with the formation of double compounds. The strong cooling prevents the undesired too rapid reaction, which leads to products not having the desired high molecular weight, and furthermore the loss in isobutylene which would occur by a It may be advantageous not to bring the catalyst into contact with the isobutylene at once but gradually. By moving the isobutylene, for example by stirring, the removal of the reaction heat is favoured and local superheating is avoided; The polymerization of isobutylene is a strongly exothermic reaction. Corresponding to the different intensity of the catalytic action of the different catalysts it is necessary to vary the intensity of cooling. For example, in the employment of the extremely active boron fluoride it is necessary to keep the temperature during the reaction below 5 C. Temperatures as low as 10 below zero C. or still lower temperatures may be employed.

The cooling may be effected externally by means of cooling baths or internally by adding to the reacting substances cold materials which have no unfavourable influence on the reaction, as for example solid carbon dioxide.

The catalysts may be employed in very small amounts; for example less than 1 per cent of catalyst is sufficient when boron fluoride is employed. It is, however, possible to use also higher percentages of catalysts, for example 3 or 5 per cent of aluminium chloride.

Solvents, such as pentane, may be present during the reaction. The resulting product is very viscous and of a from sticky to semi-solid or solid or rubber-like consistency; it is colorless and clear, soluble in liquid hydrocarbons in any proportion and may easily be depolymerized, without the formation of coke, to form gaseous and lower boiling hydrocarbons by heating, for example to a temperature of 300 C. Of particular value are the polymerized products having a molecular weight of more than 2000, as for example up to 10000 and more. The Coni'adsoncoke-test of these products is very low and not far from zero; it amounts for example to 0.01.

The following examples further illustrate the preferred preparation of the said polymerized isoolefines; the preparation of these products is, however, not restricted to the particular operations there described.

Example 1 About 0.5 part of boron fluoride is led into 100 parts of liquid isobutylene which is cooled by a bath of carbon dioxide at 80 below zero 0. The polymerization soon sets in vigorously. By in tense stirring while maintaining the cooling, the considerable heat of reaction is led away so well that the temperature does not rise above 20 below zero C. The reaction product has a mean molecular weight of 3500. It is extremely viscous, may be drawn out into threads and, even at 200 C., it is still not liquid.

Example 2 The process is similar to that in Example 1 except that before and during the leading in of boron fluoride solid carbon dioxide is thrown into the reaction material in order to maintain the temperature below from 60 to 70 below zero C. A product having a mean molecular weight of about 5000 is obtained. The product is as viscous as normal rubber masticated at 70 C. It is slightly sticky, colorless and clear.

Example 3 A 20 per cent solution of isobutylene in pentane is kept at 40 below zero C. while leading in boron fluoride. After expelling volatile constituents with steam the product has a molecular weight of 2500. The product is much more soft and more sticky than that obtained according to Ex ample 2; it is colorless and clear and may be drawn into long threads.

Example 4 A mixture of grams of isobutylene and 110 grams of normal butylene (mainly a-butylene) is polymerized as described in Example 2. After distilling off the normal butylene grams of a residue having a molecular weight of about 4000 are obtained.

Example A mixture oi. 50 grams of isobutylene and 250 grams 01 normal butylene are polymerized as described in Example 2. After distilling of! a residue of 58 grams is obtained. From this residue 11 grams may be distilled oil under a pressure of 0.1 millimetre mercury gauge and at a temperature up to 200 C., 47 grams of a product having a molecular weight of about 3000 thus being obtained.

Example -6 A mixture consisting of 900 grams of natural gas gasoline (distilling almost completely up to 60C., 60 grams of isobutylene and 290 grams of normal butylene. which mixture is liquid under a slight, super-atmospheric pressure, is polymerized as described in Example 2.

After distilling off 79 grams of a polymerization product are obtained, of which 16grams, under a pressure of 15 millimetres mercury gauge, boil. up to 200 0., and further. 18 grams boil up-to this temperature under a pressure 010.07 millimetre mercury gauge. 45 grams of a residue having a mean molecular weight of 3500 remain in the still.

The molecular weight may be increased by dc densable vapors evolved from the heating zone to return. The resulting isobutylene, when polymerized as described in Example 2 furnishes a polymerization product having a molecular weight of more than 5000.

What we claim is:-

1. A composition of matter comprising an un- For example the said polymerized hydrocarbon product boiling above 200 C. and an iso-oleiinic hydrocarbon polymer having a molecular weight of at least 1000 in. a viscosity improving amount.

2. A composition of matter comprising a petroleum lubricating oil and an iso-olefinic hydrocarbon polymer having a molecular weight of at least 3000 in a viscosity improving amount.

3. A composition of matter comprising an unpolymerized hydrocarbon product boiling about 200 C. and an isobutylene polymer having a molecular weight in excess oi 1000 in a viscosity improving amount.

4. A composition of matter comprising a pctroleum lubricating oil and a polymer of isobutylene having a molecular weight in excess of 5000 in a viscosity improving amount.

5. A composition of matter comprising troleum lubricating oil and a polymer of isobutylene having a molecular weight between about 2000 and 10,000 in a viscosity improving amount.

6. A composition of matter comprising an unpolymerized hydrocarbon product boiling above 200 C. and a polymer oi isobutylene having a molecular-weight between 2000 and 10,000 in a viscosity improving amount.

7; A composition of matter essentially comprising a parailln wax and a small amount 01 isobutylene polymer having a molecular weight of at least 1000.

8. A composition of matter essentially comprising a hydrocarbon insulating oil and a small amount of an isobutylene polymer having a molecular weight of at least 1000.

9. A composition of matter essentially comprising a wax selected from the group consisting 01 hard and soft paraflln waxes. and a polymer oi" iso-olefine having a molecular weight oif at least 1,000, the amount of polymer not exceeding that of the wax.

10. Composition according to claim 9 in which the iso-oleiine polymer is a polymer .0! isobutylene.

MICHAEL OTTO. MARTIN MUEILER-CUNRADI. 

